JP5533184B2 - Novel compound, radiation-sensitive composition, cured film and method for forming the same - Google Patents

Description

  The present invention relates to a novel compound useful as a photopolymerization initiator, a radiation-sensitive composition containing the novel compound, a cured film formed from the composition, and a method for forming the same.

  The radiation-sensitive composition can form a cured product in a large amount and easily by a coating process, and from the advantages such as easy microfabrication of the cured product, in addition to liquid crystal devices, semiconductor device production materials, etc. It is also widely used for photo-curable inks and photosensitive printing plates. Such a radiation sensitive composition typically contains a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator. In the cured product forming process, the radiation-sensitive composition is applied onto a glass substrate or the like to form a coating, and then the coating is exposed with an exposure apparatus equipped with a light source such as a mercury lamp. A cured film is formed as a cured product.

  In such a radiation-sensitive resin composition, various oxime ester compounds have been developed as photopolymerization initiators having excellent sensitivity to the wavelength of mercury lamps and capable of forming a cured film having high hardness. (See, for example, JP-T-2004-534797, JP-A-2006-30809, JP-A-2008-100755, etc.).

  However, because the conventional oxime ester compounds as described above have a slight absorption band in the visible region, a cured film obtained using these as a photopolymerization initiator is not sufficiently transparent. Absent. Therefore, such a cured film may not be applicable to a cured film that requires high transparency in the visible region, such as a liquid crystal device. Further, the oxime ester compound is not sufficiently soluble in the radiation-sensitive resin composition, and there is room for improvement.

JP-T-2004-534797 JP 2006-30809 A JP 2008-100755 A

  The present invention has been made on the basis of the circumstances as described above. In addition to having high radiation sensitivity when used as a photopolymerization initiator, it has high transparency and excellent dissolution in a radiation-sensitive composition. It aims at providing the compound provided with property, the cured film which has high transparency and surface hardness, this formation method, and the radiation sensitive composition which can form this cured film.

  The invention made to solve the above problems is a compound represented by the following formula (1).

(In formula (1), ^{R 1} is an alkyl group having 1 to 12 carbon atoms, alicyclic hydrocarbon group having 4 to 20 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, 2-furyl group, 2-furfuryl Group, 2-thienyl group, 2-thenyl group, phenyl group or naphthyl group, and part or all of the hydrogen atoms of the phenyl group or naphthyl group are alkyl groups having 1 to 6 carbon atoms, 1 to 6 carbon atoms May be substituted with an alkoxy group or a halogen atom.
R ² and R ³ are each independently an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
R ⁴ is an alicyclic hydrocarbon group, and part or all of this hydrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms. )

  The compound exhibits high radiation sensitivity when used as a photopolymerization initiator, and as a result, a cured film having an accurate pattern and sufficient surface hardness can be obtained even with a small exposure amount. Moreover, since the compound has a structure represented by the above formula (1), it has little absorption in the visible light region, is excellent in transparency, and has high transparency when used as a photopolymerization initiator. A membrane can be obtained. Furthermore, since the compound has a bulky alicyclic hydrocarbon group at the terminal, it has low crystallinity and high solubility in the radiation-sensitive composition.

In the compound, the R ¹ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, the R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, and the R ⁴ is It is good in it being a C4-C30 alicyclic hydrocarbon group which has a hydrogen atom or a C1-C4 linear alkyl group in 1st position. By introducing such a structure into the compound, the compound can be easily prepared, and the transparency and solubility in the radiation-sensitive composition can be further improved. In addition, the radiation-sensitive composition The radiation sensitivity of the product and the hardness of the resulting cured product can be further increased.

  The radiation sensitive composition of the present invention contains [A] the above compound as a photopolymerization initiator and [B] a polymerizable compound having an ethylenically unsaturated double bond. Since such a radiation sensitive composition contains the said compound, it has high radiation sensitivity and transparency. Moreover, such a radiation sensitive composition can form the cured film which has high surface hardness and transparency.

  The radiation-sensitive composition preferably further contains an alkali-soluble resin as the [C] component. When the radiation-sensitive composition contains an alkali-soluble resin, the alkali-soluble resin is soluble in the alkali used in the development process, and as a result, a high developability is expressed and the curing has an accurate pattern. A film can be formed.

  The cured film of this invention is formed from the said radiation sensitive composition. The cured film has excellent transparency and high hardness as described above.

The cured film of the present invention is
(1) A step of forming a film of the radiation-sensitive composition on a substrate,
(2) A step of irradiating at least a part of the coating formed in step (1) with radiation,
(3) It can be suitably formed by a method comprising a step of developing the film irradiated with radiation in step (2), and (4) a step of heating the film developed in step (3).

  In addition to having high radiation sensitivity when used as a photopolymerization initiator, the novel compound of the present invention has high transparency and excellent solubility in a radiation-sensitive composition. Therefore, according to the radiation-sensitive composition containing the compound of the present invention, an accurate pattern can be formed with a small exposure amount, and the formed cured film has sufficient surface hardness and excellent transparency. Therefore, for example, it can be suitably used as a protective film, an insulating film or the like for a liquid crystal device or the like.

(New compound)
The novel compound of the present invention is a compound represented by the above formula (1).
In the above formula (1), examples of the alkyl group having 1 to 12 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, n Examples include linear alkyl groups such as -octyl group and n-dodecyl group, and branched alkyl groups such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group. In these, C1-C8 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, are preferable, and a C1-C3 alkyl group is especially preferable.

In the above formula (1), examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms of R ¹ include monocyclic saturated carbonization such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Polycyclic saturated hydrocarbon groups such as hydrogen group, norbornyl group and adamantyl group, monocyclic unsaturated hydrocarbon groups such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cycloheptynyl group and cyclooctynyl group, Examples thereof include polycyclic unsaturated hydrocarbon groups such as norbornenyl group.

In the above formula (1), the haloalkyl group having 1 to 6 carbon atoms of R ¹ is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 6 carbon atoms are substituted with halogen atoms. Group, chloroethyl group, chloropropyl group, chlorobutyl group, chlorohexyl group and the like.

In the above formula (1), examples of the alkoxy group having 1 to 6 carbon atoms that is substituted with the hydrogen atom of the phenyl group or naphthyl group of R ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, Examples include butoxy group and pentyloxy group.

In the above formula (1), examples of the alicyclic hydrocarbon group of ^{R 2} and the alkyl group and 4 to 20 carbon atoms having 1 to 12 carbon atoms ^{R 3,} include the same groups as ^{R 1.} R ² and R ³ are each independently preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably a linear alkyl group having 1 to 4 carbon atoms.

In the above formula (1), as the alicyclic hydrocarbon group for R ⁴ , for example,
Monocyclic saturated hydrocarbon groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl;
A polycyclic saturated hydrocarbon group such as a norbornyl group, a dinorbornyl group, a trinorbornyl group, an adamantyl group;
Monocyclic unsaturated hydrocarbon groups such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cycloheptynyl group, cyclooctynyl group;
Examples thereof include polycyclic unsaturated hydrocarbon groups such as norbornenyl group and dinorbornenyl group. The alkyl group having 1 to 12 carbon atoms substituting a hydrogen atom of the alicyclic hydrocarbon group R ^4, include the same groups as R ^1.

R ⁴ is preferably an alicyclic hydrocarbon group forming a 6-membered ring including a carbon atom connected to a carbonyl group, such as a cyclohexane skeleton, a cyclohexene skeleton, a norbornane skeleton, a norbornene skeleton, an adamantane skeleton, or the like.

Specific examples of R ⁴ include groups represented by the following formulas (2-1) to (2-20).

Since the compound has such a bulky alicyclic hydrocarbon group as R ⁴ which is the terminal position, the compound has low crystallinity and high solubility in the radiation-sensitive composition. Further, the compound for having such an alicyclic hydrocarbon group as R ^4, while having high sensitivity to radiation, can exhibit high transparency to visible light.

As R ⁴ , an alicyclic hydrocarbon group having a hydrogen atom at the 1-position (for example, the above formulas (2-1), (2-4), (2-5), (2-10), (2 -11), (2-14), groups represented by (2-20), etc.) or a carbon number alicyclic hydrocarbon group having a linear alkyl group having 1 to 4 carbon atoms at the 1-position ( For example, the above formulas (2-2), (2-3), (2-6) to (2-9), (2-12), (2-13), (2-15) to (2-17) Is also preferred from the viewpoint of easy synthesis. Here, “position 1” means the position of the carbon atom bonded to the adjacent carbonyl group in R ^4. Having a hydrogen atom or a linear alkyl group at position 1 means bonding to the carbon atom at position 1. Having a hydrogen atom or a linear alkyl group.

  Specific examples of the compound represented by the above formula (1) include compounds represented by the following formulas (3) to (11).

In the compound, the R ¹ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, the R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, and the R ⁴ is And an alicyclic alicyclic hydrocarbon group, and particularly preferably an alicyclic hydrocarbon group having 4 to 30 carbon atoms. By being an alicyclic hydrocarbon group having such a three-dimensional structure, the production of by-products due to dioxime esterification at the time of synthesis is suppressed as compared with the case where R ⁴ is an aromatic substituent. The target compound can be obtained with high purity. Furthermore, by introducing such an alicyclic hydrocarbon group as R ⁴ into the compound, the preparation of the compound is facilitated, and transparency and solubility in the radiation-sensitive composition are further improved. In addition, the radiation sensitivity of the radiation-sensitive composition and the hardness of the resulting cured product can be increased. Specific examples of the compound having such a structure include compounds represented by the above formulas (3) to (7) and (9) to (11).

  The compound exhibits high radiation sensitivity when used as a photopolymerization initiator, and as a result, a cured film having an accurate pattern and sufficient surface hardness can be obtained with a small exposure amount. Moreover, since the said compound has a bulky alicyclic hydrocarbon group at the terminal, its crystallinity is low, and it shows high solubility with respect to a radiation sensitive composition. Furthermore, since the compound has a structure represented by the above formula (1), it has little absorption in the visible light region and is excellent in transparency, and is high when the compound is used as a photopolymerization initiator. A cured film having transparency can be obtained.

(Method for synthesizing new compounds)
It does not specifically limit as a synthesis method of the novel compound of this invention, It can synthesize | combine combining a well-known technique, For example, the following procedures can be mentioned. In the presence of aluminum chloride, a carboxylic acid halide or anhydride having an aliphatic hydrocarbon group corresponding to R ⁴ is reacted with 3-acyl-9-alkylcarbazole to obtain a diketone body. This diketone body is dissolved in N, N-dimethylacetamide, and only a non-cyclic alkylketone part is selectively oximed with hydroxylammonium chloride under basic conditions, and finally the hydroxyl group is acetylated. Can be obtained.

Examples of the carboxylic acid halide having an aliphatic hydrocarbon group corresponding to R ⁴ include cycloalkane carboxylic acid chlorides such as cyclohexane carboxylic acid chloride, and 5-norbornene-2-methyl-2-carboxylic acid chloride. And carboxylic acid chlorides having a polycyclic structure such as tricyclo [5.2.1.0 ^2,6 ] decan-8-ylcarboxylic acid chloride and 1-adamantanecarboxylic acid chloride.

(Radiation sensitive composition)
The radiation-sensitive composition of the present invention contains [A] the above compound as a photopolymerization initiator and [B] a polymerizable compound having an ethylenically unsaturated double bond, and [C] alkali as a suitable component. Soluble resin and other optional components [D] Radiation sensitive polymerization initiator other than the above [A] component (hereinafter also simply referred to as “other radiation sensitive polymerization initiator”), [E] polyfunctional epoxy A compound, [F] adhesion assistant, [G] surfactant and the like may be contained.

([A] Photopolymerization initiator)
The photopolymerization initiator of the component [A] used in the radiation sensitive composition is a compound represented by the above formula (1). Here, the photopolymerization initiator refers to a component capable of generating an active species capable of initiating polymerization of the polymerizable compound of the component [B] by irradiation with visible light, ultraviolet light, far ultraviolet light or the like. About the said compound, since it is as above-mentioned, description is abbreviate | omitted here.

([B] polymerizable compound having an ethylenically unsaturated double bond)
Preferred examples of the polymerizable compound having an ethylenically unsaturated double bond used in the radiation-sensitive composition include monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or higher (meth) acrylate. Can be mentioned. By using these compounds in the radiation-sensitive composition, a cured film in which transparency and surface hardness are highly balanced can be formed.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl- Examples include 2-hydroxypropyl phthalate. Examples of these monofunctional (meth) acrylate commercial products include Aronix M-101, M-111, M-114 (manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S (Japan) Kayaku Co., Ltd.), Biscoat 158, 2311 (Osaka Organic Chemical Co., Ltd.) and the like.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, and bisphenoxyethanol full orange (meth) acrylate. As a commercial item of these bifunctional (meth) acrylates, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R- 604 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 260, 312, and 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, mono- [3- (3- (meth) acryloyloxy-2,2-bis- (meth) acryloyloxymethyl-propoxy) -2 , 2-bis- (meth) acryloyloxymethyl-propyl] ester, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like. Commercially available products of these tri- or higher functional (meth) acrylates include, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, and M- 8060, TO-756 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 295, 300, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Of these polymerizable compounds having an ethylenically unsaturated double bond, a tri- or higher functional (meth) acrylate is preferably used from the viewpoint of curability of the radiation-sensitive composition. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid mono- [3- (3- (meth) acryloyloxy-2,2-bis -(Meth) acryloyloxymethyl-propoxy) -2,2-bis- (meth) acryloyloxymethyl-propyl] ester, succinic acid-modified pentaerythritol tri (meth) acrylate is particularly preferred. These polymerizable compounds having an ethylenically unsaturated double bond can be used alone or in admixture of two or more.

  Although the usage-amount of the polymeric compound which has an ethylenically unsaturated bond of the [B] component in the said radiation sensitive composition is not specifically limited, With respect to 1 mass part of photoinitiators of a [A] component. The amount is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass. By making the usage-amount of such a polymeric compound into the said range, the radiation sensitive composition in which radiation sensitivity and transparency of the cured film obtained were highly balanced can be obtained.

([C] alkali-soluble resin)
The [C] alkali-soluble resin that may be contained in the radiation-sensitive composition is one that is soluble in an alkali developer used in the development processing step of the radiation-sensitive composition containing the component. There is no particular limitation. As such an alkali-soluble resin, an alkali-soluble resin having a carboxyl group is preferable, and (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “compound (a1)”. ) ”And an unsaturated compound other than (a2) and (a1) (hereinafter referred to as“ compound (a2) ”) (hereinafter referred to as copolymer [α]). .

Specific examples of the compound (a1) include
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

  Among these compounds (a1), acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an alkaline developer. Acid, maleic anhydride and the like are preferable.

  In the copolymer [α], the compound (a1) can be used alone or in admixture of two or more. In the copolymer [α], the content of the repeating unit derived from the compound (a1) is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and particularly preferably 8 to 40% by mass. By setting the content of the repeating unit derived from the compound (a1) to 5 to 60% by mass, a radiation-sensitive composition in which various properties such as radiation sensitivity and developability are balanced at a higher level can be obtained.

Specific examples of the compound (a2) include
Alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate) Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;
Methacrylic acid hydroxyalkyl esters such as methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester;
Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;

Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate and diethyl fumarate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, p-methoxystyrene;
Conjugated diene compounds such as 1,3-butadiene and isoprene;
Other examples include acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

Among these compounds (a2), from the viewpoint of copolymerization reactivity, n-butyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, styrene, P-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, methacrylic acid 2-hydroxyethyl ester and the like are preferable.

  In the copolymer [α], the compound (a2) can be used alone or in admixture of two or more. In the copolymer [α], the content of the repeating unit derived from the compound (a2) is preferably 10 to 70% by mass, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass. By setting the content of the repeating unit of the compound (a2) to 10 to 70% by mass, it becomes easy to control the molecular weight of the copolymer, and the radiation-sensitive composition in which developability, radiation sensitivity, etc. are balanced at a higher level. A thing is obtained.

  The copolymer [α] can be produced by polymerizing the constituent monomers in a suitable solvent in the presence of a radical polymerization initiator. As a solvent used for such polymerization, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate ester and the like are preferable. These solvents can be used alone or in admixture of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2 , 2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobis (2-methylpropionate), An azo compound such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be given. These radical polymerization initiators can be used alone or in admixture of two or more.

  The polystyrene-converted mass average molecular weight (hereinafter referred to as “Mw”) of the copolymer [α] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50, 000. By setting Mw of the copolymer [α] to 2,000 to 100,000, a radiation-sensitive composition in which developability, radiation sensitivity and the like are balanced at a higher level, and a cured film having high heat resistance are obtained. be able to.

  The amount of the alkali-soluble resin [C] component used in the radiation-sensitive composition is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts per 1 part by weight of the photopolymerization initiator [A]. Part by mass. By making the usage-amount of alkali-soluble resin into the said range, the radiation sensitive composition excellent in developability can be obtained.

([D] Other radiation-sensitive polymerization initiators)
In addition to the [A] component, other radiation-sensitive polymerization initiators can be added to the radiation-sensitive composition as the [D] component. The radiation-sensitive polymerization initiator is not particularly limited as long as it is a component that generates an active species capable of initiating polymerization of a polymerizable compound having an ethylenically unsaturated double bond in response to radiation. Examples of such other radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like.

  Specific examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like (except for the component [A]).

  Among these, preferable O-acyloxime compounds include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime). These O-acyloxime compounds can be used alone or in admixture of two or more.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

  Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-Morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like can be mentioned.

  Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like.

  Of these acetophenone compounds, α-aminoketone compounds are preferred, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one is particularly preferred. These acetophenone compounds can be used alone or in admixture of two or more.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 Examples include '-biimidazole.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole Is particularly preferred. These biimidazole compounds can be used alone or in admixture of two or more.

  In the radiation-sensitive composition of the present invention, when a biimidazole compound is used as the radiation-sensitive polymerization initiator of the [D] component, an aliphatic or aromatic compound having a dialkylamino group ( Hereinafter, it is referred to as “amino sensitizer”.

  Examples of such amino sensitizers include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferred. The amino sensitizers can be used alone or in admixture of two or more.

  Furthermore, when a biimidazole compound and an amino sensitizer are used in combination in the radiation-sensitive composition, a thiol compound can be added as a hydrogen radical donor. A biimidazole compound is sensitized by an amino sensitizer and cleaved to generate an imidazole radical, but may not exhibit high polymerization initiation ability as it is. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from the thiol compound to the imidazole radical. As a result, the imidazole radical is converted to neutral imidazole, and a component having a sulfur radical with a high polymerization initiation ability is generated, thereby forming a cured film having a high surface hardness even at a low radiation dose. Can do.

Specific examples of such thiol compounds include
Aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole;
Aliphatic monothiol compounds such as 3-mercaptopropionic acid and methyl 3-mercaptopropionate;
Bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified. Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

  When a biimidazole compound and an amino sensitizer are used in combination, the use amount of the amino sensitizer is preferably 0.1 to 50 parts by mass, more preferably 100 parts by mass of the biimidazole compound. Is 1-20 parts by mass. By making the usage-amount of an amino-type sensitizer into 0.1-50 mass parts, the cure reactivity at the time of exposure of a radiation sensitive composition can improve, and the surface hardness of the cured film obtained can be raised.

  Moreover, when using together a biimidazole compound, an amino type sensitizer, and a thiol compound, as the usage-amount of a thiol compound, Preferably it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More Preferably it is 1-20 mass parts. By making the usage-amount of a thiol compound into 0.1-50 mass parts, the surface hardness of the obtained cured film can be improved.

  It is preferable that the said radiation sensitive composition contains at least 1 sort (s) selected from the group which consists of an O-acyl oxime compound and an acetophenone compound as a radiation sensitive polymerization initiator of [D] component. The radiation-sensitive composition contains at least one selected from the group consisting of an O-acyloxime compound and an acetophenone compound as a radiation-sensitive polymerization initiator of the component [D], and a biimidazole compound. It may be.

  The use amount of the radiation sensitive polymerization initiator of the [D] component in the radiation sensitive composition is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 1 part by mass of the [A] component. -5 parts by mass. By setting the amount of component [D] used in the above range, the radiation-sensitive composition can form a cured film having a high radiation sensitivity and a sufficient surface hardness even in the case of a low exposure amount. .

([E] polyfunctional epoxy compound)
[E] The polyfunctional epoxy compound can be added to the radiation-sensitive composition in order to increase the polymerization reactivity and further improve the surface hardness of the cured film formed from the radiation-sensitive composition. As the polyfunctional epoxy compound, a cationic polymerizable compound having two or more epoxy groups in one molecule is used.

  Specific examples of such cationically polymerizable compounds having two or more epoxy groups in one molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether. Bisphenol polyglycidyl ethers such as hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, Polyglycidyl ether of polyhydric alcohol such as trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ters; Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; 2 per molecule Compounds having one or more 3,4-epoxycyclohexyl groups; phenol novolac type epoxy resins such as bisphenol A novolac type epoxy resins; cresol novolac type epoxy resins; polyphenol type epoxy resins; cyclic aliphatic epoxy resins; Examples include diglycidyl esters of acids; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil, and the like. Of these cationically polymerizable compounds having two or more epoxy groups in one molecule, phenol novolac type epoxy resins and polyphenol type epoxy resins are preferred.

  Specific examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3 , 4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4) of ethylene glycol -Epoxycyclohexylmethyl) ether , Ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', may be mentioned 4'-epoxycyclohexane carboxylate.

  Commercially available compounds having two or more epoxy groups in one molecule include, for example, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 as bisphenol A type epoxy resins. (Japan Epoxy Resin Co., Ltd.); Epicoat 807 (Japan Epoxy Resin Co., Ltd.); bisphenol F type epoxy resin; Epicote 152, 154 as phenol novolac type epoxy resin (bisphenol A novolac type epoxy resin, etc.) 157S65 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN 201, id 202 (manufactured by Nippon Kayaku Co., Ltd.); medicine( )), Epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.); as a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (manufactured by Japan Epoxy Resin Co., Ltd.); CY-175 as a cyclic aliphatic epoxy resin, 177, 179, Araldite CY-182, 192, 184 (manufactured by Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206 (manufactured by U.C.C.), Shodyne 509 ( Showa Denko Co., Ltd.), Epicron 200, 400 (Dainippon Ink Co., Ltd.), Epicoat 871, 872 (Japan Epoxy Resin Co., Ltd.), ED-5661, 5662 (Celanese Coating Co., Ltd.) Epolite 100M as aliphatic polyglycidyl ether (Manufactured by Kyoeisha Chemical Co.), Epiol TMP (manufactured by NOF Corporation) and the like.

  These [E] component polyfunctional epoxy compounds can be used alone or in admixture of two or more. The use amount of the polyfunctional epoxy compound of the [E] component in the radiation sensitive composition is preferably 0.05 to 10 parts by mass with respect to 1 part by mass of the photopolymerization initiator of the [A] component. Preferably it is 0.1-5 mass parts. By making the usage-amount of an [E] component into 0.05-10 mass parts, while improving polymerization reactivity, the surface hardness of the formed cured film can be maintained at a high level.

([F] Adhesion aid)
The [F] component adhesion assistant can be used to further improve the adhesion between the resulting cured film and the substrate. As such an adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group is preferable. Specific examples of the adhesion assistant include γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. A silane etc. can be mentioned. These adhesion assistants can be used alone or in admixture of two or more.

  The usage-amount of the adhesion promoter of the [F] component in the said radiation sensitive composition is 0.05-10 mass parts with respect to 1 mass part of [A] component, More preferably, it is 0.05-8 mass. Part. By making the usage-amount of adhesion | attachment adjuvant into the said range, pattern formation ability can be maintained at a high level, improving the adhesiveness of the cured film with respect to a board | substrate.

([G] surfactant)
The surfactant as component [G] can be used to further improve the film-forming property of the radiation-sensitive composition. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and other surfactants.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable. Examples of fluorosurfactants include 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2- Tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2) 2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2- Tetrafluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2 2,3,3,9,9,10,10-decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether) Fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoroalkylpolyoxyethylene ethers, perfluoroalkylpolyoxyethanol, perfluoroalkylalkoxylates, carboxylic acid fluoroalkyl esters, and the like.

  Commercially available fluorosurfactants include, for example, BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. F476 (above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, -171, -430, -431 (above, Sumitomo 3M Limited), Surflon S-112, -113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, Asahi Glass Co., Ltd.) Manufactured), Ftop EF301, 303, 352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), Footent FT-100, -110, -140A,- 50, the same -250, the -251, the -300, the -310, the -400S, Ftergent FTX-218, the -251 (or, Co. NEOS), and the like.

  Specific examples of the silicone-based surfactant are commercially available product names such as Toresilicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, and SH-190. 193, the same SZ-6032, the same SF-8428, the same DC-57, the same DC-190, the SH 8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF- 4445, TSF-4446, TSF-4460, TSF-4252 (manufactured by GE Toshiba Silicone Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  These [G] component surfactants can be used alone or in admixture of two or more. The usage-amount of surfactant of [G] component in the said radiation sensitive composition is 0.001-1 mass part with respect to 1 mass part of [A] component, More preferably, it is 0.005-0. 5 parts by mass. By making the usage-amount of surfactant into the said range, the coating nonuniformity at the time of forming a film on a board | substrate can be reduced.

(Preparation of radiation-sensitive composition)
The radiation-sensitive composition of the present invention includes the above-mentioned [A] photopolymerization initiator, [B] a polymerizable compound having an ethylenically unsaturated double bond, and other optional additions as described above. Prepared by mixing the ingredients uniformly. This radiation-sensitive composition is preferably used in a solution state after being dissolved in an appropriate solvent. For example, by mixing [A] a photopolymerization initiator and [B] a polymerizable compound having an ethylenically unsaturated double bond, and other components optionally added, in a solvent at a predetermined ratio, A radiation-sensitive composition in a solution state can be prepared.

  As the solvent used for the preparation of the radiation-sensitive composition, [A] a photopolymerization initiator, [B] a polymerizable compound having an ethylenically unsaturated double bond, and other optional components are homogeneous. Those that dissolve in the aqueous solution and do not react with each component are used. As such a solvent, the thing similar to what was illustrated above as a solvent which can be used in order to manufacture a [C] alkali-soluble resin can be mentioned.

  Among such solvents, for example, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether from the viewpoint of solubility of each component, non-reactivity with each component, ease of film formation, and the like. , Propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, and 3-methoxybutanol can be particularly preferably used. . These solvents may be used alone or in a combination of two or more.

  When preparing the radiation-sensitive composition as a solution, the solid content concentration (components other than the solvent in the composition solution, that is, the total amount of the above-mentioned [A] component and [B] component and other optional components) The ratio can be set to an arbitrary concentration (for example, 5 to 50% by mass) according to the purpose of use, a desired film thickness value, and the like. The solution of the radiation-sensitive composition thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 to 0.5 μm.

(Cured film)
The cured film formed from the radiation-sensitive composition of the present invention has high surface hardness and excellent transparency, as will be apparent from the examples described later. Such a cured film can be suitably used for technical applications that require high surface hardness and transparency. For example, it can be suitably used as a protective film, an insulating film, and a pattern forming material for liquid crystal devices and semiconductor devices.

(Method for forming cured film)
Next, a method for forming a cured film using the radiation-sensitive composition of the present invention will be described. A method for forming a cured film using the radiation-sensitive composition includes at least the following steps (1) to (4) in the order described below. Step (3) can be performed when pattern formation is required.

That is, the method of forming the cured film is as follows:
(1) A step of forming a film of the radiation-sensitive composition of the present invention on a substrate,
(2) A step of irradiating at least a part of the coating formed in step (1) with radiation,
(3) A step of developing the film irradiated with radiation in the step (2), and (4) a step of heating the film developed in the step (3).

  Hereinafter, each of these steps will be described sequentially.

(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate is not specifically limited as a board | substrate used here, A transparent substrate, a metal substrate, etc. are mentioned. Examples of the transparent substrate include glass substrates and resin substrates. Specific examples thereof include glass substrates such as soda lime glass and alkali-free glass; polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, A resin substrate made of a plastic such as polyimide can be given. A transparent conductive film can be formed on one side of such a transparent substrate, and a film of the radiation sensitive composition can be formed on the transparent conductive film.

As the transparent conductive film provided on one side of the transparent substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), ITO made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) A film etc. can be mentioned.

  In the case of forming a film by a coating method, the film can be formed preferably by heating (pre-baking) the coated surface after coating a solution of the radiation-sensitive composition on the transparent conductive film. The solid content concentration of the composition solution used for the coating method is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 15 to 35% by mass. The coating method of the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet coating method or the like is adopted. can do. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable.

  The pre-baking conditions vary depending on the types and blending ratios of the components, but are preferably about 70 to 120 ° C. for about 1 to 15 minutes. The film thickness of the film after pre-baking is preferably 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

(2) Step of irradiating at least part of the coating formed in step (1) Next, radiation is applied to at least part of the formed coating. At this time, when irradiating only a part of the film, for example, the irradiation can be performed through a photomask having a predetermined pattern.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 to 550 nm is preferable.

Radiation irradiation amount (exposure amount) is preferably 100 to 5,000 J / m ² , as a value obtained by measuring the intensity of irradiated radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.). preferably from 200~3,000J / ^{m 2.}

(3) Step of developing the film irradiated with radiation in step (2) Next, by developing the film after irradiation, unnecessary portions are removed to form a predetermined pattern.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and alkalis (basic compounds) such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to these aqueous alkali solutions. The concentration of the alkali in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 to 180 seconds at room temperature.

(4) Step of heating the coating developed in step (3) After the above development treatment, the patterned coating is preferably washed with running water for 30 to 90 seconds and then air-dried with compressed air or compressed nitrogen. can do. Subsequently, the obtained pattern-shaped film is subjected to a predetermined temperature, for example, 100 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, and 30 in the oven by a suitable heating device such as a hot plate or an oven. A cured film having high surface hardness can be obtained by heating (post-baking) for ˜180 minutes.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention further in detail, this invention is not limited to these Examples.

<Synthesis Example of Compound [A] Component (Photopolymerization Initiator)>
[Example 1] (Synthesis of Compound (A-1))
Compound (A-1) (compound represented by the above formula (3)) as a final product was synthesized according to the following synthesis scheme.

Step (I): Synthesis of Intermediate (a) 8.5 g (61.5 mmol) of 5-norbornene-2-carboxylic acid was added to a 300 ml eggplant-shaped flask, dissolved in 60 ml of ethanol, and purged with nitrogen. Next, 0.5 g of 5% palladium-carbon was added, followed by catalytic reduction with hydrogen at 40 ° C. and normal pressure. After stirring for 16 hours, the filter paper and celite were placed on a suction filtration device, and suction filtration was performed. The filtrate was distilled off under reduced pressure to obtain 8.6 g of intermediate (a).

When ¹ H-NMR of this intermediate (a) was measured, it was as follows.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 2.74 ppm, 2.60 ppm, (1H in combination of two isomer peaks), 2.36 ppm (1H), 2.06 ppm (1H), 1 .7 to 1.2 ppm (8H)

Step (II): Synthesis of Intermediate (b) To a 300 ml eggplant-shaped flask, 14 g (10 mmol) of intermediate (a) and 16 ml (220 mmol) of thionyl chloride were added, stirred at room temperature 25 ° C., then N, N-dimethylformamide (0.1 ml) was added, and the mixture was further stirred for 20 hours. The reaction solution was distilled off under reduced pressure to obtain 15.9 g of intermediate (b).

Step (III): Synthesis of Intermediate (c) To a 1000 ml eggplant-shaped flask, 24 g (101 mmol) of 3-acetyl-9-ethylcarbazole was added and dissolved in 400 ml of methylene chloride, and 43 g (350 mmol) of aluminum chloride was added to this solution. Was added, and the mixture was ice-cooled, and the temperature of the reaction solution was lowered to 10 ° C. To this reaction solution, 35 g (220 mol) of intermediate (b) was dissolved in 50 ml of methylene chloride and added dropwise. During the dropping, the reaction solution temperature was kept at 10 to 20 ° C. After completion of dropping, the reaction solution was stirred at 20 ° C. for 20 hours. The reaction solution was quenched into 150 g of ice water and stirred, and further 200 ml of water was added and extracted three times with 200 ml of chloroform. The organic layer was collected, washed with saturated sodium bicarbonate, then with distilled water, and the solvent was distilled off under reduced pressure to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 25.5 g of intermediate (c).

When ¹ H-NMR of this compound was measured, it was as follows.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 8.80 ppm, 8.76 ppm (1H in combination of two isomer peaks), 8.57 ppm, 8.54 ppm (peak alignment of two isomers) 1H), 8.21 ppm, 8.18 ppm (1H combined with two isomer peaks), 7.97 ppm, 7.95 ppm (1H combined with two isomer peaks), 7.44 ppm (2H) 4.40 ppm (2H), 3.92 ppm, 3.40 ppm (1H combined with 2 isomer peaks), 2.74 ppm, 2.60 ppm (1H combined with 2 isomer peaks), 2 .36 ppm (1H), 2.30 ppm (3H), 2.06 ppm (1H), 1.7 to 1.2 ppm (10H)

Step (IV): Synthesis of Intermediate (d) In a 500 ml eggplant-shaped flask, 25.5 g (70.9 mmol) of Intermediate (c) was added and dissolved in 250 ml of dimethylacetamide, and 4.5 g (112 mmol) of sodium hydroxide was added. And stirred at 65 ° C. for 1 hour. Next, 9.0 g (125 mmol) of hydroxylammonium chloride was added to the reaction solution, the temperature was raised to 90 ° C., and the mixture was stirred at this temperature for 1 hour. Next, the reaction solution was cooled to room temperature, 200 ml of distilled water was added, and the mixture was extracted 3 times with 200 ml of ethyl acetate. The organic layer was collected and washed with 200 ml of distilled water, and the organic layer was distilled off under reduced pressure to obtain an intermediate (d).

Step (V): Synthesis of Compound (A-1) To a 500 ml eggplant-shaped flask, 25.5 g (70.9 mmol) of the intermediate (d) was added and dissolved in 100 ml of n-butyl acetate, and 10 g (98 mmol) of acetic anhydride. And stirred at 90 ° C. for 1 hour. The reaction solution was cooled to room temperature, 200 ml of water was added, the organic layer was extracted, and further extracted twice with 100 ml of n-butyl acetate. The organic layers were combined, washed with 200 ml of distilled water, and distilled under reduced pressure to obtain a crude product. This crude product was purified by silica gel column chromatography to obtain 21.1 g of compound (A-1).

When ¹ H-NMR, FT-IR, mass spectrometry, and UV of this compound were measured, it was as follows.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 8.80 ppm, 8.76 ppm (1H in combination of two isomer peaks), 8.57 ppm, 8.54 ppm (peak alignment of two isomers) 1H), 8.21 ppm, 8.18 ppm (1H combined with two isomer peaks), 7.97 ppm, 7.95 ppm (1H combined with two isomer peaks), 7.44 ppm (2H) 4.40 ppm (2H), 3.92 ppm, 3.40 ppm (1H combined with two isomer peaks), 2.74 ppm, 2.60 ppm (1H combined with two isomer peaks), 2. 53ppm (3H), 2.36ppm (1H), 2.30ppm (3H), 2.06ppm (1H), 1.7-1.2ppm (10H)
FT-IR (KBr): 3072 cm ⁻¹ , 2956 cm ⁻¹ , 2869 cm ⁻¹ , 2821 cm ⁻¹ , 1764 cm ⁻¹ , 1666 cm ⁻¹ , 1627 cm ⁻¹ , 1592 cm ⁻¹
LC-MS [M + H]: m / z = 417
UV (λmax): 258 nm, 292 nm

[Example 2] (Synthesis of Compound (A-2))
In step (I) in the synthesis scheme of compound (A-1), except that catalytic reduction with hydrogen was not performed, the reaction was performed in the same manner as in Example 1, except that compound (A-2) in Example 2 (above A compound represented by the formula (4) was obtained.

It was as follows when ¹ H-NMR, FT-IR, mass spectrometry, and UV of the compound (A-2) were measured.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 8.81 ppm, 8.75 ppm (1H in combination of two isomer peaks), 8.57 ppm, 8.54 ppm (peak combination of two isomers) 1H), 8.23 ppm, 8.14 ppm (1H combined with two isomer peaks), 7.96 ppm, 7.95 ppm (1H combined with two isomer peaks), 7.44 ppm (2H) 5.98 ppm (2H), 4.40 ppm (2H), 3.94 ppm, 3.40 ppm (1H in combination of the two isomer peaks), 2.77 ppm, 2.64 ppm (peaks of the two isomers) 1H), 2.54 ppm (3H), 2.37 ppm (1H), 2.30 ppm (3H), 2.06 ppm (1H), 1.7 to 1.2 ppm (8H)
FT-IR (KBr): 3075 cm ⁻¹ , 2950 cm ⁻¹ , 28609 cm ⁻¹ , 2828 cm ⁻¹ , 1770 cm ⁻¹ , 1658 cm ⁻¹ , 1615 cm ⁻¹ , 1584 cm ⁻¹
LC-MS [M + H]: m / z = 415
UV (λmax): 265 nm, 298 nm

[Example 3] (Synthesis of Compound (A-3))
Example 1 except that 5-norbornene-2-methyl-2-carboxylic acid was used instead of 5-norbornene-2-carboxylic acid in Step (I) in the synthesis scheme of the compound (A-1). In the same manner as in Example 1, the compound (A-3) of Example 3 (compound represented by the above formula (5)) was obtained.

¹ H-NMR of Compound (A-3), FT- IR, mass spectrometry, was measured to UV, it was as follows.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 8.84 ppm, 8.72 ppm (1H in combination of two isomer peaks), 8.54 ppm, 8.53 ppm (peak alignment of two isomers) 1H), 8.23 ppm, 8.15 ppm (1H combined with two isomer peaks), 7.97 ppm, 7.95 ppm (1H combined with two isomer peaks), 7.44 ppm (2H) 4.40 ppm (2H), 3.94 ppm, 3.40 ppm (1H combined with 2 isomer peaks), 2.74 ppm, 2.63 ppm (1H combined with 2 isomer peaks), 2. 58ppm (3H), 2.34ppm (1H), 2.36ppm (3H), 2.01ppm (1H), 1.7-1.2ppm (12H)
FT-IR (KBr): 3074 cm ⁻¹ , 2958 cm ⁻¹ , 2875 cm ⁻¹ , 2832 cm ⁻¹ , 1764 cm ⁻¹ , 1668 cm ⁻¹ , 1620 cm ⁻¹ , 1597 cm ⁻¹
LC-MS [M + H]: m / z = 430
UV (λmax): 257 nm, 290 nm

[Example 4] (Synthesis of Compound (A-4))
Example 1 except that cyclohexanecarboxylic acid was used in place of 5-norbornene-2-carboxylic acid and catalytic reduction with hydrogen was not performed in step (I) in the synthesis scheme of compound (A-1). In the same manner as in Example 4, the compound (A-4) of Example 4 (compound represented by the above formula (6)) was obtained.

It was as follows when ¹ H-NMR, FT-IR, mass spectrometry, and UV of the compound (A-4) were measured.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 8.86 ppm, 8.77 ppm (1H in combination of two isomer peaks), 8.53 ppm, 8.56 ppm (peak combination of two isomers) 1H), 8.23 ppm, 8.18 ppm (1H combined with two isomer peaks), 7.91 ppm, 7.94 ppm (1H combined with two isomer peaks), 7.42 ppm (2H) 4.45 ppm (2H), 3.98 ppm, 3.43 ppm (1H combined with 2 isomer peaks), 2.76 ppm, 2.65 ppm (1H combined with 2 isomer peaks), 2. 65 ppm (3H), 2.36 ppm (1H), 2.38 ppm (3H), 2.10 ppm (1H), 1.7-1.2 ppm (10H)
^{FT-IR (KBr): 3078cm} -1, 2963cm -1, 2878cm -1, 2835cm-1,1766cm -1, 1658cm -1, 1615cm -1, 1590cm -1
LC-MS [M + H]: m / z = 404
UV (λmax): 260 nm, 288 nm

[Example 5] (Synthesis of Compound (A-5))
In step (I) in the synthesis scheme of the compound (A-1), tricyclo [5.2.1.0 ^2,6 ] decan-8-ylcarboxylic acid was used instead of 5-norbornene-2-carboxylic acid. The compound (A-5) (the compound represented by the above formula (7)) of Example 5 was obtained in the same manner as in Example 1 except that catalytic reduction with hydrogen was not performed.

It was as follows when ¹ H-NMR, FT-IR, mass spectrometry, and UV of the compound (A-4) were measured.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 8.92 ppm, 8.69 ppm (1H in combination of two isomer peaks), 8.54 ppm, 8.56 ppm (peak combination of two isomers) 1H), 8.28 ppm, 8.15 ppm (1H combined with two isomer peaks), 7.92 ppm, 7.92 ppm (1H combined with two isomer peaks), 7.44 ppm (2H) 4.41 ppm (2H), 3.92 ppm, 3.42 ppm (1H combined with 2 isomer peaks), 2.74 ppm, 2.61 ppm (1H combined with 2 isomer peaks), 2. 67ppm (3H), 2.32ppm (1H), 2.32ppm (3H), 2.14ppm (1H), 1.7-1.1ppm (14H)
FT-IR (KBr): 3083 cm ⁻¹ , 2970 cm ⁻¹ , 2872 cm ⁻¹ , 2838 cm ⁻¹ , 1761 cm ⁻¹ , 1652 cm ⁻¹ , 1612 cm ⁻¹ , 1598 cm ⁻¹
LC-MS [M + H]: m / z = 456
UV (λmax): 263 nm, 291 nm

[Example 6] (Synthesis of Compound (A-6))
In step (I) in the synthesis scheme of the compound (A-1), 1-adamantanecarboxylic acid was used instead of 5-norbornene-2-carboxylic acid, and catalytic reduction with hydrogen was not performed, and step (II) ), Except that 3-octanoyl-9-methylcarbazole was used instead of 3-acetyl-9-ethylcarbazole, the same procedure as in Example 1 was carried out, and the compound (A-6) of Example 6 (above A compound represented by the formula (8) was obtained.

¹ H-NMR of Compound (A-6), FT- IR, mass spectrometry, was measured to UV, it was as follows.
¹ H-NMR (solvent: CDCl ₃ ) chemical shift δ: 8.92 ppm, 8.69 ppm (1H in combination of two isomer peaks), 8.53 ppm, 8.52 ppm (peak combination of two isomers) 1H), 8.23 ppm, 8.10 ppm (1H combined with two isomer peaks), 7.92 ppm, 7.92 ppm (1H combined with two isomer peaks), 7.48 ppm (2H) 4.41 ppm (2H), 3.95 ppm, 3.43 ppm (1H combined with 2 isomer peaks), 2.74 ppm, 2.61 ppm (1H combined with 2 isomer peaks), 2. 62 ppm (3H), 2.35 ppm (1H), 2.36 ppm (3H), 2.18 ppm (1H), 1.7-1.1 ppm (16H)
FT-IR (KBr): 3088 cm ⁻¹ , 2980 cm ⁻¹ , 2878 cm ⁻¹ , 2840 cm ⁻¹ , 1765 cm ⁻¹ , 1658 cm ⁻¹ , 1622 cm ⁻¹ , 1560 cm ⁻¹
LC-MS [M + H]: m / z = 578
UV (λmax): 256 nm, 287 nm

<Synthesis example of alkali-soluble resin (copolymer) of component [C]>
[Synthesis Example C-1] (Synthesis of Copolymer (C-1))
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of propylene glycol monomethyl ether acetate, followed by 18 parts by mass of methacrylic acid and tricyclomethacrylate [5 .2.1.0 ^2,6 ] Decan-8-yl 25 parts by mass, styrene 5 parts by mass, methacrylic acid 2-hydroxyethyl ester 30 parts by mass, and benzyl methacrylate 22 parts by mass were charged with nitrogen. Next, while gently stirring, the temperature of the solution is raised to 70 ° C., and this temperature is maintained for 5 hours for polymerization to obtain a copolymer (C-1) solution having a solid content concentration of 28.8%. It was. It was 13,000 when Mw was measured about the obtained copolymer (C-1) using the following apparatuses and conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran

<Evaluation of solubility of photopolymerization initiator in organic solvent>
Compounds (A-1) to (A-6) and Compound (D-1) (ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- ( Solubility of O-acetyloxime: a compound represented by the following formula (12) (“Irgacure OXE02” manufactured by Ciba Specialty Chemicals) in 100 g of PGMEA (propylene glycol monomethyl ether acetate) or 100 g of cyclohexanone at 20 ° C. The results are shown in Table 1.

<Preparation of radiation-sensitive composition>
[Example 7]
1 part by mass (solid content) of the compound (A-1) of Example 1 as the [A] component, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as the [B] component (manufactured by Nippon Kayaku Co., Ltd.) "KAYARAD DPHA"), 100 parts by mass, 5 parts by mass of γ-glycidoxypropyltrimethoxysilane as the [F] component, and fluorine surfactant ("FTX-218" manufactured by Neos Co., Ltd.) as the [G] component ) 0.3 parts by mass was mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm. A solution of the composition was prepared.

[Examples 8 to 16 and Comparative Examples 1 to 5]
The radiation sensitive resin compositions of Examples 8 to 16 and Comparative Examples 1 to 5 were the same as Example 1 except that the types and amounts as shown in Table 1 were used as the components [A] to [G]. A product solution was prepared.

  In Table 1, the abbreviations for the components [B], [D], [E], [F] and [G] mean the following compounds, respectively.

B-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ((“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.))
B-2: Succinic acid-modified pentaerythritol triacrylate (“Aronix TO-756” manufactured by Toagosei Co., Ltd.)
D-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (manufactured by Ciba Specialty Chemicals Irgacure OXE02 ")
D-2: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (“Irgacure” manufactured by Ciba Specialty Chemicals) 379 ")
D-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“Irgacure 907” manufactured by Ciba Specialty Chemicals)
E-1: Phenol novolac type epoxy resin (“Epicoat 152” manufactured by Japan Epoxy Resin Co., Ltd.)
E-2: Bisphenol A novolac type epoxy resin (“Epicoat 157S65” manufactured by Japan Epoxy Resin Co., Ltd.)
F-1: γ-Glycidoxypropyltrimethoxysilane G-1: Fluorosurfactant (“FTX-218” manufactured by Neos Co., Ltd.)

<Characteristic evaluation of radiation-sensitive composition and cured film>
Evaluation of the radiation sensitive compositions of Examples 7 to 16 and Comparative Examples 1 to 5 prepared as described above, and cured films formed therefrom were performed as follows. The evaluation results are shown in Table 2.

(1) Evaluation of radiation sensitivity of radiation-sensitive composition After applying a solution of the radiation-sensitive composition on a non-alkali glass substrate with a spinner, pre-baking on a hot plate at 80 ° C for 3 minutes, A coating (film thickness: 4.0 μm) of the radiation composition was formed. On the obtained film, it exposed using the photomask which has two or more round residual patterns with a diameter of 15 micrometers. At this time, a predetermined gap (exposure gap) was provided between the coating surface and the photomask. Next, using a high pressure mercury lamp, the coating film was exposed through the photomask while changing the exposure amount. Subsequently, using a potassium hydroxide aqueous solution with a concentration of 0.05 mass%, development was performed by a shower method at 25 ° C. for 20 seconds, followed by washing with pure water for 1 minute, and further in an oven at 230 ° C. A round pattern was formed by post-baking for 20 minutes. The height of this circular pattern after post-baking was measured using a laser microscope (VK-8500 manufactured by Keyence). The residual film ratio (%) was obtained by applying this value to the following equation.
Residual film ratio (%) = (pattern height after post-baking / initial film thickness 4.0 μm) × 100

The exposure amount at which the remaining film ratio was 90% or more was defined as the radiation sensitivity of the radiation-sensitive composition. When the exposure amount is 900 J / m ² or less, it can be said that the radiation sensitivity is good.

(2) Evaluation of transparency of cured film Except that a photomask was not used and the exposure amount was 600 J / m ² , in the same manner as in “(1) Evaluation of radiation sensitivity of radiation-sensitive composition”, A cured film was formed on a glass substrate (“NA35 (manufactured by NH Techno Glass Co., Ltd.)”). Using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.)", the light transmittance of the glass substrate having this cured film is 400 to 800 nm with the glass substrate having no protective film as the reference side. Measured at a wavelength in the range of. The value of the minimum light transmittance at that time was used as the evaluation of the transparency of the cured film. When this value is 95% or more, it can be said that the transparency of the cured film is good.

(3) Measurement of Pencil Hardness (Surface Hardness) of Cured Film About a substrate having a cured film formed in the same manner as in the above “(2) Evaluation of transparency of cured film”, 8.4.1 of JISK-5400-1990. The pencil hardness (surface hardness) of the cured film was measured by a pencil scratch test. When this value is 3H or more, it can be said that the surface hardness of the cured film is good.

  As shown in Table 1, the compounds (A-1) to (A-6) of the present invention synthesized in Examples 1 to 6 have high solubility with respect to each of PGMEA and cyclohexanone as solvents. I understand that. Moreover, as Table 2 shows, the radiation sensitive composition of Examples 7-16 containing the compound (A-1)-(A-6) of this invention as a photoinitiator is Comparative Examples 1-1. It was found that the radiation sensitivity was equal to or higher than 5, and the transparency and surface hardness of the resulting cured film were excellent.

  When used as a photopolymerization initiator, the novel compound of the present invention exhibits high radiation sensitivity, has excellent solubility, and can form a cured film having high transparency and sufficient surface hardness. Therefore, it is extremely useful as a component of the radiation-sensitive composition.

Claims (6)

A compound represented by the following formula (1).

(In formula (1), ^{R 1} is an alkyl group having 1 to 12 carbon atoms, alicyclic hydrocarbon group having 4 to 20 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, 2-furyl group, 2-furfuryl Group, 2-thienyl group, 2-thenyl group, phenyl group or naphthyl group, and part or all of the hydrogen atoms of the phenyl group or naphthyl group are alkyl groups having 1 to 6 carbon atoms, 1 to 6 carbon atoms May be substituted with an alkoxy group or a halogen atom.
R ² and R ³ are each independently an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
R ⁴ is an alicyclic hydrocarbon group, and part or all of this hydrogen atom may be substituted with an alkyl group having 1 to 12 carbon atoms. ) R ¹ is an alkyl group having 1 to 8 carbon atoms or a phenyl group,
R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms,
The compound according to claim 1, wherein R ⁴ is a C 4-30 alicyclic hydrocarbon group having a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms at the 1-position. [A] A radiation-sensitive composition containing the compound according to claim 1 or 2 as a photopolymerization initiator, and [B] a polymerizable compound having an ethylenically unsaturated double bond.   [C] The radiation-sensitive composition according to claim 3, further comprising an alkali-soluble resin.   A cured film formed from the radiation-sensitive composition according to claim 3 or 4. (1) The process of forming the film of the radiation sensitive composition of Claim 3 or Claim 4 on a board | substrate,
(2) A step of irradiating at least a part of the coating formed in step (1) with radiation,
(3) A method for forming a cured film, comprising: a step of developing the coating irradiated with radiation in step (2); and (4) a step of heating the coating developed in step (3).